Self-Supported PtAuP Alloy Nanotube Arrays with Enhanced Activity and Stability for Methanol Electro-Oxidation.

Inhibiting CO formation can more directly address the problem of CO poisoning during methanol electro-oxidation. In this study, 1D self-supported porous PtAuP alloy nanotube arrays (ANTAs) are synthesized via a facile electro-codeposition approach and present enhanced activity and improved resistance to CO poisoning through inhibiting CO formation (non-CO pathway) during the methanol oxidation reaction in acidic medium. This well-controlled Pt-/transition metal-/nonmetal ternary nanostructure exhibits a specific electroactivity twice as great as that of PtAu alloy nanotube arrays and Pt/C. At the same time, PtAuP ANTAs show a higher ratio of forward peak current density (If ) to backward peak current density (Ib ) (2.34) than PtAu ANTAs (1.27) and Pt/C (0.78). The prominent If /Ib value of PtAuP ANTAs indicates that most of the intermediate species are electro-oxidized to carbon dioxide in the forward scan, which highlights the high electroactivity for methanol electro-oxidation.

[1]  L. Gu,et al.  Ultra-small Tetrametallic Pt-Pd-Rh-Ag Nanoframes with Tunable Behavior for Direct Formic Acid/Methanol Oxidation. , 2016, Small.

[2]  L. Gu,et al.  Interfacial electronic effects control the reaction selectivity of platinum catalysts. , 2016, Nature materials.

[3]  N. Zheng,et al.  Carbon Monoxide-Assisted Synthesis of Ultrathin PtCu3 Alloy Wavy Nanowires and Their Enhanced Electrocatalysis. , 2016, Small.

[4]  F. Gao,et al.  General synthesis of binary PtM and ternary PtM1M2 alloy nanoparticles on graphene as advanced electrocatalysts for methanol oxidation , 2015 .

[5]  Haihui Wang,et al.  Highly stable PtP alloy nanotube arrays as a catalyst for the oxygen reduction reaction in acidic medium† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c5sc00124b Click here for additional data file. , 2015, Chemical science.

[6]  G. Botton,et al.  Pt–Au–Co Alloy Electrocatalysts Demonstrating Enhanced Activity and Durability toward the Oxygen Reduction Reaction , 2015 .

[7]  Abhijit Dutta,et al.  Ternary NiAuPt Nanoparticles on Reduced Graphene Oxide as Catalysts toward the Electrochemical Oxidation Reaction of Ethanol , 2015 .

[8]  Shichao Zhang,et al.  Application of Carbon Supported Ptcore–Aushell Nanoparticles in Methanol Electrooxidation , 2014 .

[9]  D. Rider,et al.  Block Copolymer Templated Synthesis of Core–Shell PtAu Bimetallic Nanocatalysts for the Methanol Oxidation Reaction , 2014 .

[10]  Abdullah M. Asiri,et al.  Self-supported Cu3P nanowire arrays as an integrated high-performance three-dimensional cathode for generating hydrogen from water. , 2014, Angewandte Chemie.

[11]  Jin Wang,et al.  Dendritic Au/Pt and Au/PtCu nanowires with enhanced electrocatalytic activity for methanol electrooxidation. , 2014, Small.

[12]  Zhen Liu,et al.  Free-Standing Pt–Au Hollow Nanourchins with Enhanced Activity and Stability for Catalytic Methanol Oxidation , 2014 .

[13]  Yingchao Yu,et al.  Synthesis of structurally ordered Pt3Ti and Pt3V nanoparticles as methanol oxidation catalysts. , 2014, Journal of the American Chemical Society.

[14]  Minghui Yang,et al.  Mesoporous Ti(0.5)Cr(0.5)N supported PdAg nanoalloy as highly active and stable catalysts for the electro-oxidation of formic acid and methanol. , 2014, ACS nano.

[15]  G. Fu,et al.  Autocatalysis and selective oxidative etching induced synthesis of platinum-copper bimetallic alloy nanodendrites electrocatalysts. , 2014, ACS applied materials & interfaces.

[16]  Changpeng Liu,et al.  Ni2P enhances the activity and durability of the Pt anode catalyst in direct methanol fuel cells , 2014 .

[17]  Wei Zhang,et al.  Hollow spheres of iron carbide nanoparticles encased in graphitic layers as oxygen reduction catalysts. , 2014, Angewandte Chemie.

[18]  Z. Wang,et al.  Core/shell Au/CuPt nanoparticles and their dual electrocatalysis for both reduction and oxidation reactions. , 2014, Journal of the American Chemical Society.

[19]  R. Webster,et al.  Newly developed stepwise electroless deposition enables a remarkably facile synthesis of highly active and stable amorphous Pd nanoparticle electrocatalysts for oxygen reduction reaction. , 2014, Journal of the American Chemical Society.

[20]  Changpeng Liu,et al.  An effective Pd-Ni(2)P/C anode catalyst for direct formic acid fuel cells. , 2014, Angewandte Chemie.

[21]  X. Duan,et al.  Monodisperse Cu@PtCu nanocrystals and their conversion into hollow-PtCu nanostructures for methanol oxidation , 2013 .

[22]  Chang Ming Li,et al.  Self-assembled phosphomolybdic acid–polyaniline–graphene composite-supported efficient catalyst towards methanol oxidation , 2013 .

[23]  Younan Xia,et al.  Enhancing the catalytic and electrocatalytic properties of Pt-based catalysts by forming bimetallic nanocrystals with Pd. , 2012, Chemical Society reviews.

[24]  L. Qu,et al.  Newly‐Designed Complex Ternary Pt/PdCu Nanoboxes Anchored on Three‐Dimensional Graphene Framework for Highly Efficient Ethanol Oxidation , 2012, Advanced materials.

[25]  Yawen Tang,et al.  Platinum–Cobalt alloy networks for methanol oxidation electrocatalysis , 2012 .

[26]  S. Choi,et al.  Shape- and Composition-Sensitive Activity of Pt and PtAu Catalysts for Formic Acid Electrooxidation , 2012 .

[27]  Jin Luo,et al.  Pt-Au alloying at the nanoscale. , 2012, Nano letters.

[28]  Chengzhou Zhu,et al.  Facile synthesis of trimetallic AuPtPd alloy nanowires and their catalysis for ethanol electrooxidation , 2012 .

[29]  Malcolm L. H. Green,et al.  Electron promotion by surface functional groups of single wall carbon nanotubes to overlying metal particles in a fuel-cell catalyst. , 2012, Angewandte Chemie.

[30]  D. Ma,et al.  Preparation of PtAu Alloy Colloids by Laser Ablation in Solution and Their Characterization , 2012 .

[31]  Chengzhou Zhu,et al.  PdM (M = Pt, Au) Bimetallic Alloy Nanowires with Enhanced Electrocatalytic Activity for Electro‐oxidation of Small Molecules , 2012, Advanced materials.

[32]  Y. Tong,et al.  Porous Pt-Ni-P composite nanotube arrays: highly electroactive and durable catalysts for methanol electrooxidation. , 2012, Journal of the American Chemical Society.

[33]  Shouheng Sun,et al.  Structure-induced enhancement in electrooxidation of trimetallic FePtAu nanoparticles. , 2012, Journal of the American Chemical Society.

[34]  Shigang Sun,et al.  Alloy tetrahexahedral Pd–Pt catalysts: enhancing significantly the catalytic activity by synergy effect of high-index facets and electronic structure , 2012 .

[35]  N. Zheng,et al.  Small Adsorbate‐Assisted Shape Control of Pd and Pt Nanocrystals , 2012, Advanced materials.

[36]  Dongju Zhang,et al.  Theoretical Study of Methanol Oxidation on the PtAu(111) Bimetallic Surface: CO Pathway vs Non-CO Pathway , 2012 .

[37]  Ping Liu,et al.  Highly stable Pt monolayer on PdAu nanoparticle electrocatalysts for the oxygen reduction reaction , 2012, Nature Communications.

[38]  V. Climent,et al.  The role of the surface structure in the oxidation mechanism of methanol , 2011 .

[39]  M. Yin,et al.  Inhibiting CO formation by adjusting surface composition in PtAu alloys for methanol electrooxidation. , 2011, Chemical communications.

[40]  G. Jackson,et al.  Tuning the CO-tolerance of Pt-Fe bimetallic nanoparticle electrocatalysts through architectural control , 2011 .

[41]  Yuyan Shao,et al.  Graphene Decorated with PtAu Alloy Nanoparticles: Facile Synthesis and Promising Application for Formic Acid Oxidation , 2011 .

[42]  Jie Yu,et al.  Promotion by hydrous ruthenium oxide of platinum for methanol electro-oxidation , 2010 .

[43]  W. Cai,et al.  Ultralow‐Platinum‐Loading High‐Performance Nanoporous Electrocatalysts with Nanoengineered Surface Structures , 2010, Advanced materials.

[44]  Gaixiu Yang,et al.  Preparation of carbon supported Pd–P catalyst with high content of element phosphorus and its electrocatalytic performance for formic acid oxidation , 2010 .

[45]  Lifeng Liu,et al.  Nanoporous pt-co alloy nanowires: fabrication, characterization, and electrocatalytic properties. , 2009, Nano letters.

[46]  M. Mavrikakis,et al.  Structure sensitivity of methanol electrooxidation on transition metals. , 2009, Journal of the American Chemical Society.

[47]  J. Tiwari,et al.  Facile approach to the synthesis of 3D platinum nanoflowers and their electrochemical characteristics , 2009 .

[48]  Zhenmeng Peng,et al.  PtAu bimetallic heteronanostructures made by post-synthesis modification of Pt-on-Au nanoparticles , 2009 .

[49]  M. Ballauff,et al.  Stable Bimetallic Gold–Platinum Nanoparticles Immobilized on Spherical Polyelectrolyte Brushes: Synthesis, Characterization, and Application for the Oxidation of Alcohols , 2008 .

[50]  Z. Wen,et al.  Template Synthesis of Aligned Carbon Nanotube Arrays using Glucose as a Carbon Source: Pt Decoration of Inner and Outer Nanotube Surfaces for Fuel‐Cell Catalysts , 2008 .

[51]  X. Gong,et al.  Decomposition pathways of methanol on the PtAu(111) bimetallic surface: a first-principles study. , 2008, The Journal of chemical physics.

[52]  Hee-Young Park,et al.  Surface Structure of Pt-Modified Au Nanoparticles and Electrocatalytic Activity in Formic Acid Electro-Oxidation , 2007 .

[53]  X. Xue,et al.  Enhancement of the electrooxidation of ethanol on Pt–Sn–P/C catalysts prepared by chemical deposition process , 2007 .

[54]  J. Fierro,et al.  Influence of the preparation route of bimetallic Pt-Au nanoparticle electrocatalysts for the oxygen reduction reaction , 2007 .

[55]  K. Sasaki,et al.  Stabilization of Platinum Oxygen-Reduction Electrocatalysts Using Gold Clusters , 2007, Science.

[56]  Weijiang Zhou,et al.  Preparation of carbon-supported core-shell Au-Pt nanoparticles for methanol oxidation reaction: The promotional effect of the Au core. , 2006, The journal of physical chemistry. B.

[57]  Keonkuk Kim,et al.  A PtAu Nanoparticle Electrocatalyst for Methanol Electro- oxidation in Direct Methanol Fuel Cells , 2006 .

[58]  X. Xue,et al.  Novel chemical synthesis of Pt–Ru–P electrocatalysts by hypophosphite deposition for enhanced methanol oxidation and CO tolerance in direct methanol fuel cell , 2006 .

[59]  G. Jackson,et al.  Enhanced CO tolerance for hydrogen activation in Au-Pt dendritic heteroaggregate nanostructures. , 2006, Journal of the American Chemical Society.

[60]  J. Moulijn,et al.  The mechanism of low-temperature CO oxidation with Au/Fe2O3 catalysts : a combined Mossbauer, FT-IR, and TAP reactor study , 2005 .

[61]  M. S. Chen,et al.  The Structure of Catalytically Active Gold on Titania , 2004, Science.

[62]  L. Kiwi-Minsker,et al.  Highly dispersed gold on activated carbon fibers for low-temperature CO oxidation , 2004 .

[63]  M. Watanabe,et al.  In-Situ ATR-FTIR Spectroscopic Study of Electro-oxidation of Methanol and Adsorbed CO at Pt−Ru Alloy , 2004 .

[64]  S. Ye,et al.  Formate, an active intermediate for direct oxidation of methanol on pt electrode. , 2003, Journal of the American Chemical Society.

[65]  T. Iwasita Electrocatalysis of methanol oxidation , 2002 .

[66]  M. J. Weaver,et al.  Electrocatalytic Pathways on Carbon-Supported Platinum Nanoparticles: Comparison of Particle-Size-Dependent Rates of Methanol, Formic Acid, and Formaldehyde Electrooxidation , 2002 .

[67]  P. Ross,et al.  Surface science studies of model fuel cell electrocatalysts , 2002 .

[68]  Antonino S. Aricò,et al.  DMFCs: From Fundamental Aspects to Technology Development , 2001 .

[69]  Seong-Soo Kim,et al.  Methanol behavior in direct methanol fuel cells. , 2008, Angewandte Chemie.

[70]  J. Lee,et al.  Segmented Pt/Ru, Pt/Ni, and Pt/RuNi nanorods as model bifunctional catalysts for methanol oxidation. , 2006, Small.